WO2015146962A1 - 吸着材及び結晶性シリコチタネートの製造方法 - Google Patents

吸着材及び結晶性シリコチタネートの製造方法 Download PDF

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WO2015146962A1
WO2015146962A1 PCT/JP2015/058864 JP2015058864W WO2015146962A1 WO 2015146962 A1 WO2015146962 A1 WO 2015146962A1 JP 2015058864 W JP2015058864 W JP 2015058864W WO 2015146962 A1 WO2015146962 A1 WO 2015146962A1
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crystalline silicotitanate
adsorbent
sodium
crystalline
mixed gel
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PCT/JP2015/058864
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English (en)
French (fr)
Japanese (ja)
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慎介 宮部
木ノ瀬　豊
政博 菊池
坂本　剛
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日本化学工業株式会社
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Priority to EP15768946.4A priority Critical patent/EP3098817A4/de
Priority to CA2939521A priority patent/CA2939521A1/en
Priority to US14/787,516 priority patent/US9486776B2/en
Priority to KR1020167023545A priority patent/KR20160138951A/ko
Priority to RU2016137781A priority patent/RU2016137781A/ru
Priority to CN201580011122.3A priority patent/CN106062885B/zh
Publication of WO2015146962A1 publication Critical patent/WO2015146962A1/ja
Priority to US15/284,020 priority patent/US9675957B2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28023—Fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

Definitions

  • the present invention relates to an adsorbent that can selectively and efficiently separate and recover cesium or strontium in seawater, and a method for producing crystalline silicotitanate that can be suitably used for the adsorbent.
  • coprecipitation treatment is known as a treatment technique for wastewater containing radioactive substances (see Patent Document 1 below).
  • the coprecipitation treatment is not effective and is currently being adsorbed and removed by an inorganic adsorbent such as zeolite (see Patent Document 2 below).
  • Non-Patent Document 1 When radioactive cesium and radioactive strontium flow into seawater, an increase in the sodium concentration of seawater components acts to suppress the ion exchange reaction between cesium and the adsorbent (see Non-Patent Document 1 below). The problem is known.
  • Crystalline silicotitanate is one of the inorganic adsorbents studied so far for the adsorption of cesium and / or strontium. Crystalline silicotitanates are known to have a plurality of types of compositions such as those with a Ti / Si ratio of 1: 1, 5:12, and 2: 1. It is known that there is crystalline silicotitanate in which is 4: 3.
  • Non-Patent Document 2 discloses that products 3B and 3C produced by hydrothermal treatment using an alkoxide Ti (OET) 4 as a Ti source and colloidal silica as a Si source are three-dimensional from the X-ray diffraction pattern.
  • OET alkoxide Ti
  • the crystalline silicotitanate having this structure ideally has a composition represented by M 4 Ti 4 Si 3 O 16 (M is Na, K, etc.). It is reported that the crystalline silicotitanate having this structure is named Grace titanium silicate (GTS-1).
  • GTS-1 Grace titanium silicate
  • Non-Patent Document 3 describes that a crystalline silicotitanate having a Ti / Si ratio of 4: 3 was produced by subjecting a mixed solution having a Ti / Si ratio of 0.32 to hydrothermal synthesis. ing. This document describes that the synthesized crystalline silicotitanate has strontium ion exchange capacity.
  • an object of the present invention is to provide an adsorbent having high adsorption performance of cesium and strontium even in seawater, and an industrially advantageous production method of crystalline silicotitanate effective as the adsorbent.
  • the present inventor has high adsorption performance of cesium and strontium from seawater when the crystalline silicotitanate having the specific composition contains a specific titanate. I found out. Furthermore, the present inventors added a silicic acid source, a sodium compound and / or potassium compound, titanium tetrachloride, and water to obtain a mixed gel having a specific ratio of Ti: Si. By hydrothermally reacting the obtained mixed gel, crystalline silicotitanate useful as an adsorbent for cesium and strontium from seawater, in particular, crystalline silicotitanate containing the specific titanate described above can be obtained efficiently. I found out that
  • the present invention has the general formula: Na 4 Ti 4 Si 3 O 16 .nH 2 O, (Na x K (1-x) ) 4 Ti 4 Si 3 O 16 .nH 2 O and K 4 Ti 4 Si 3 O At least one selected from crystalline silicotitanates represented by 16 ⁇ nH 2 O (wherein x represents a number greater than 0 and less than 1 and n represents a number from 0 to 8); ; Na 4 Ti 9 O 20 ⁇ mH 2 O, (Na y K (1-y)) 4 Ti 9 O 20 ⁇ mH 2 O , and K 4 Ti 9 O 20 ⁇ mH 2 O ( in these formulas, y is
  • the present invention provides a cesium or strontium adsorbent containing at least one selected from titanates represented by the formula: a number greater than 0 and less than 1 and m represents a number from 0 to 10.
  • the present invention also provides a general formula: Na 4 Ti 4 Si 3 O 16 .nH 2 O, (Na x K (1-x) ) 4 Ti 4 Si 3 O 16 .nH 2 O and K 4 Ti 4 Si 3.
  • a second step of hydrothermal reaction of the mixed gel obtained in the first step, In the first step, crystalline silicon is added, wherein a silicic acid source and titanium tetrachloride are added so that the molar ratio of Ti and Si contained in the mixed gel is Ti / Si 0.5 or more and 3.0 or less.
  • a method for producing a titanate is provided.
  • adsorbent excellent in adsorption and removal characteristics of cesium and strontium even in seawater and crystalline silicotitanate effective as the adsorbent can be produced by an industrially advantageous method.
  • FIG. 1 is an X-ray diffraction chart of the adsorbent (crystalline silicotitanate) obtained in Example 1 of the present invention.
  • FIG. 2 is an X-ray diffraction chart after baseline correction of the adsorbent (crystalline silicotitanate) obtained in Example 1 of the present invention.
  • FIG. 3 is an X-ray diffraction chart after baseline correction of the adsorbent (crystalline silicotitanate) obtained in Example 2 of the present invention.
  • FIG. 4 is an X-ray diffraction chart after baseline correction of the adsorbent (crystalline silicotitanate) obtained in Example 3 of the present invention.
  • FIG. 1 is an X-ray diffraction chart of the adsorbent (crystalline silicotitanate) obtained in Example 1 of the present invention.
  • FIG. 2 is an X-ray diffraction chart after baseline correction of the adsorbent (crystalline silicotitanate) obtained in Example 1 of the present
  • FIG. 5 is an X-ray diffraction chart after baseline correction of the adsorbent (crystalline silicotitanate) obtained in Comparative Example 1 of the present invention.
  • FIG. 6 is an X-ray diffraction chart after baseline correction of the adsorbent (crystalline silicotitanate) obtained in Example 6 of the present invention.
  • Adsorbent of the present invention have the general formula; Na 4 Ti 4 Si 3 O 16 ⁇ nH 2 O, (Na x K (1-x)) 4 Ti 4 Si 3 O 16 ⁇ nH 2 O and K 4 Ti 4 Si At least one selected from crystalline silicotitanates represented by 3 O 16 ⁇ nH 2 O (wherein x represents a number greater than 0 and less than 1 and n represents a number from 0 to 8) Unless otherwise specified, it is simply referred to as “crystalline silicotitanate” or “the crystalline silicotitanate”) and a general formula; Na 4 Ti 9 O 20 .mH 2 O, (Na y K (1-y) ) 4 Ti 9 O 20 ⁇ mH 2 O and K 4 Ti 9 O 20 ⁇ mH 2 O (in these formulas, y represents a number greater than 0 and less than 1, and m represents a number from 0 to 10).
  • titanates At least one selected from titanates (hereinafter referred to simply as “titanate” or “the titanate” unless otherwise specified). .
  • the present invention is characterized in that the crystalline silicotitanate and the titanate are stably coexisted to form an adsorbent.
  • the adsorbent of the present invention has excellent cesium and strontium adsorption removal performance due to this characteristic.
  • Examples of the form of the adsorbent of the present invention include powders, granules, and moldings other than granules (spherical or cylindrical), and the like is preferably powder or granules.
  • the powdery adsorbent can be obtained, for example, by producing the crystalline silicotitanate containing the titanate as a byproduct by a production method described later.
  • a granular adsorbent can be obtained by granulating a powder adsorbent by the granulation process mentioned later.
  • the adsorbent of the present invention reflects a coexistence of the crystalline silicotitanate and the titanate stably, and has a specific diffraction peak pattern when measured by X-ray diffraction. This diffraction peak pattern will be described in detail below.
  • X-ray diffraction measurement using Cu—K ⁇ as an X-ray source and a diffraction angle (2 ⁇ ) in the range of 5 to 80 °, one or more peaks of the crystalline silicotitanate are observed.
  • a diffraction angle (2 ⁇ ) in the range of 5 to 80 °
  • the adsorbent of the present invention has the highest intensity peak (hereinafter also referred to as a main peak) among the crystalline silicotitanate peaks when X-ray diffraction measurement is performed in the range of the above-mentioned radiation source and diffraction angle.
  • the ratio of the main peak height of the titanate is preferably 5% or more and 70% or less, more preferably 5% or more and 60% or less, and more preferably 5% or more and 50% or less. Further preferred.
  • crystalline silicotitanate is produced by a production method described later, and at that time, a silicic acid source, a sodium compound, a potassium compound, and titanium tetrachloride are produced.
  • the material ratio may be adjusted.
  • the peak height ratio is calculated based on a diffraction peak pattern obtained by performing baseline correction on a diffraction peak pattern obtained by actual X-ray diffraction measurement. This baseline correction is performed by the sonneveld-visser method.
  • the peak height is obtained from the diffraction peak pattern as follows. First, a straight line is obtained by connecting two bottom points of one peak. Then, a perpendicular line is drawn from the peak apex to intersect with the straight line, and the distance between the obtained intersection and the peak apex is defined as the peak height.
  • the peak detected at 8 to 10 ° is derived from the titanate whose crystal orientation is (010) and m in the general formula (2) is 5 to 7. Therefore, such an adsorbent contains a large amount of hydrated salt having m of 5 to 7 as the titanate.
  • crystalline silicotitanate is produced using a production method described later, and at that time, a silicic acid source and a sodium compound are produced.
  • the material ratio of potassium compound, titanium tetrachloride, etc. may be adjusted.
  • the titanate is further in the range of 27 to 29 ° and / or 47 to 49 °. It is preferable that the peak is detected. Further, these peaks preferably have a height of 10% or more and 70% or less with respect to the height of the main peak of the titanate described above.
  • the main peak of the crystalline silicotitanate is preferably observed in a diffraction angle (2 ⁇ ) range of 10 to 13 °.
  • the peak detected in this range is derived from the crystalline silicotitanate having a crystal orientation of (0, 1, 0) and n of 5-7.
  • a crystalline silicotitanate peak is detected.
  • these peaks preferably have a height of 5% or more and 40% or less with respect to the height of the main peak of the crystalline silicotitanate described above.
  • the molar ratio of the titanate to the crystalline silicotitanate obtained by composition analysis is preferably 1: 0.25 to 0.45, and 1: 0 More preferably, it is 30 to 0.40, and further preferably 1: 0.35 to 0.38. Specifically, this molar ratio is determined by the following method.
  • the content (mass%) of SiO 2 and TiO 2 in the adsorbent is calculated by calculating by the SQX method which is a semi-quantitative analysis method.
  • the crystalline silicotitanates are Na 4 Ti 4 Si 3 O 16 .nH 2 O, (Na x K (1-x) ) 4 Ti 4 Si 3 O 16 .nH 2 O and K 4 Ti 4 Si 3 O 16.
  • ⁇ nH selected from crystalline Shirikochitaneto represented by 2 O is at least one.
  • the crystalline silicotitanate may be composed of only one of these crystalline silicotitanates, or may be a mixture of two or more.
  • crystalline Shirikochitaneto represented by 4 Ti 4 Si 3 O 16 ⁇ nH 2 O is a single compound x takes a single value Alternatively, x may be a mixture of two values. In the crystalline silicotitanate, n may take only one value, or n may take two or more values.
  • the crystalline silicotitanate contains Na 4 Ti 4 Si 3 O 16 .nH 2 O and K 4 Ti 4 Si 3 O 16 .nH 2 O, or (Na x K (1-x) ) 4 Ti 4
  • Si 3 O 16 .nH 2 O is contained, the crystalline silicotitanate tends to have a high degree of crystallinity, and this can improve the performance of the adsorbent, particularly the adsorption performance of cesium.
  • the crystalline silicotitanate contains a crystalline silicotitanate other than A 4 Ti 4 Si 3 O 16 .nH 2 O (where A is Na, K or Na and K). May be.
  • the crystalline silicotitanate is crystalline having at least a molar ratio of Ti and Si of 1: 1. It is preferred that the silicotitanate peak and the crystalline silicotitanate peak with a molar ratio of Ti and Si of 5:12 are not observed.
  • the peak of only A 4 Ti 4 Si 3 O 16 .nH 2 O is observed when the adsorbent of the present invention is measured by X-ray diffraction at a diffraction angle (2 ⁇ ) of 5 to 80 °. .
  • 2 ⁇ 25 ° which is a peak of titanium oxide is not detected.
  • the titanates are represented by Na 4 Ti 9 O 20 ⁇ mH 2 O, (Na y K (1-y) ) 4 Ti 9 O 20 ⁇ mH 2 O and K 4 Ti 9 O 20 ⁇ mH 2 O. At least one selected from the group consisting of titanates.
  • the titanate may be composed of only one of these titanates or a mixture of two or more.
  • y may be a single compound which takes a single value However, it may be a mixture of y having two values. In the titanate, m may take only one value, or m may take two or more values.
  • the adsorbent of the present invention contains a titanate other than A 4 Ti 9 O 20 .mH 2 O (where A is Na, K or Na and K), such as Na 2 Ti 3 O 7.
  • a 4 Ti 9 O 20 .mH 2 O (where A is Na, K or Na and K)
  • a 4 Ti 9 O 20 ⁇ mH 2 O Preferably only a diffraction peak is observed.
  • the titanate or comprises Na 4 Ti 9 O 20 ⁇ mH 2 O , and K 4 Ti 9 O 20 ⁇ mH 2 O, or (Na y K (1-y )) 4 Ti 9 O 20 ⁇ mH 2 O It is preferable from the viewpoint of further improving the selective adsorptivity of cesium and strontium.
  • the value of x in the crystalline silicotitanate represented by 16 ⁇ nH 2 O may be the same or different.
  • the values of x and y are each independently more than 0 and less than 1, and any value can be adopted within this range.
  • the amount ratio of Na and K in crystalline silicotitanate and the amount ratio of Na and K in titanate can be estimated to some extent from the amount ratio of Na and K in the adsorbent of the present invention.
  • the amount ratio of Na and K in the adsorbent of the present invention is preferably such that the ratio of the number of moles of K is 3 to 50, where the total number of moles of Na and K is 100. It is more preferable. This ratio is determined by, for example, the contents (mass of Na 2 O and K 2 O in the adsorbent by measuring all elements described in (a) of ⁇ Molecular ratio of crystalline silicotitanate: titanate> described above. %) Can be calculated
  • the adsorbent of the present invention described above can be manufactured by the method for manufacturing the crystalline silicotitanate of the present invention described below.
  • the method for producing the crystalline silicotitanate of the present invention includes a general formula as a by-product in addition to the crystalline silicotitanate represented by the above general formula; Na 4 Ti 9 O 20 .mH 2 O, (Na y K (1-y)) 4 Ti 9 O 20 ⁇ mH 2 O , and K 4 Ti 9 O 20 ⁇ mH 2 O ( in these formulas, y represents a number from 0 to less ultra 1, m is 0 to 10
  • the adsorbent of the present invention can be produced by producing at least one selected from titanates represented by: However, the production method of the present invention includes a method that does not produce the titanate.
  • the first step in the method for producing crystalline silicotitanate of the present invention is a step of producing a mixed gel by mixing a silicic acid source, a sodium compound and / or potassium compound, titanium tetrachloride, and water.
  • Examples of the silicic acid source used in the first step include sodium silicate. Moreover, the active silicic acid obtained by carrying out cation exchange of the alkali silicate (namely, alkali metal salt of silicic acid) is also mentioned.
  • Active silicic acid is obtained by cation exchange by bringing an aqueous alkali silicate solution into contact with, for example, a cation exchange resin.
  • a sodium silicate aqueous solution usually called water glass (water glass No. 1 to No. 4 etc.) is preferably used. This is relatively inexpensive and can be easily obtained.
  • an aqueous potassium silicate solution is suitable as a raw material.
  • the aqueous alkali silicate solution is diluted with water as necessary.
  • the cation exchange resin used when preparing the active silicic acid can be appropriately selected from known ones and is not particularly limited.
  • the alkali silicate aqueous solution is diluted with water so that the silica has a concentration of 3% by mass or more and 10% by mass or less.
  • a strong acidic or weakly acidic cation exchange resin to dealkalize. Further, if necessary, it can be deanioned by contacting with an OH type strongly basic anion exchange resin.
  • an active silicic acid aqueous solution is prepared.
  • various proposals have already been made, and any known contact conditions can be adopted in the present invention.
  • Non-Patent Document 3 While highly dispersed SiO 2 powder is used as a silicon source in Non-Patent Document 3, it is possible to use sodium silicate or activated silicic acid as a silicic acid source in the production method of the present invention. This has the advantage that the manufacturing cost can be reduced.
  • Examples of the sodium compound used in the first step include sodium hydroxide and sodium carbonate.
  • sodium hydroxide when sodium carbonate is used, carbon dioxide gas is generated. Therefore, it is preferable to use sodium hydroxide that does not generate such gas from the viewpoint of smoothly promoting the neutralization reaction.
  • a crystalline silicotitanate represented by Na 4 Ti 4 Si 3 O 16 .nH 2 O can be obtained as a crystalline silicotitanate. It can.
  • sodium titanate represented by Na 4 Ti 9 O 20 ⁇ mH 2 O can be obtained as a by-product.
  • a sodium compound and a potassium compound are used in the first step, whether Na 4 Ti 4 Si 3 O 16 .nH 2 O and K 4 Ti 4 Si 3 O 16 .nH 2 O are included as crystalline silicotitanate.
  • a material containing (Na x K (1-x) ) 4 Ti 4 Si 3 O 16 .nH 2 O can be obtained.
  • Na 4 Ti 9 O 20 .mH 2 O and K 4 Ti 9 O 20 .mH 2 O are contained as by-product titanates, or (Na y K (1-y) ) 4 Ti 9 O Those containing 20 ⁇ mH 2 O can be obtained.
  • the ratio of the number of moles of the potassium compound to the total number of moles of the sodium compound and the potassium compound is preferably 3 to 50%, and preferably 5 to 30%. More preferably.
  • Examples of the potassium compound used in the first step include potassium hydroxide and potassium carbonate, and potassium hydroxide is preferred for the same reason as the sodium compound.
  • titanium tetrachloride is used as a titanium source.
  • another titanium compound such as titanium oxide is used as the titanium source, as illustrated in Comparative Example 1 described later, unreacted titanium oxide remains or the molar ratio of Ti: Si is 4: 3. Crystalline silicotitanate other than crystalline silicotitanate is easily formed. Therefore, in the present invention, titanium tetrachloride is used as the titanium source.
  • the addition amount of the silicic acid source and titanium tetrachloride may be set to an amount in which Ti / Si, which is the molar ratio of Ti derived from titanium tetrachloride and Si derived from the silicic acid source in the mixed gel, becomes a specific ratio. It is one of the characteristics of the manufacturing method of crystalline silicotitanate of the invention.
  • Ti / Si which is the molar ratio of Ti derived from titanium tetrachloride and Si derived from the silicic acid source in the mixed gel. It is one of the characteristics of the manufacturing method of crystalline silicotitanate of the invention.
  • titanium tetrachloride is used as the titanium source, but the silicate source and titanium tetrachloride are added to the mixed solution in such an amount that the Ti / Si ratio is 0.32.
  • the silicic acid source and titanium tetrachloride are added in such an amount that the Ti / Si ratio is 0.5 or more and 3.0 or less.
  • the Ti / Si ratio in the mixed gel is preferably 1.0 or more and 3.0 or less, more preferably 1.5 or more and 2.5 or less, and 1.8 or more and 2.2 or less. More preferably, it is as follows.
  • the Ti / Si ratio is within the above range is that the obtained crystalline silicotitanate tends to contain a specific titanate as a by-product, and the adsorbent of the present invention described above is suitable. It is also preferable in that it can be produced.
  • a crystalline silicotitanate when usually used as an adsorbent, it is common to adopt a composition that does not contain by-products.
  • one of the preferred embodiments of the production method of the present invention is relatively Surprisingly, the adsorption performance of cesium and strontium is improved by adopting a high Ti / Si ratio and generating by-products.
  • a ′ represents Na and K.
  • the yield of the desired crystalline silicotitanate can be increased to a satisfactory level, and the molar ratio of Ti and Si Can effectively prevent the production of a 1: 1 product.
  • These ranges are also preferable from the viewpoint of by-producing the titanate.
  • the titanium tetrachloride used in the first step can be used without particular limitation as long as it is industrially available.
  • the silicic acid source, sodium compound, potassium compound, and titanium tetrachloride can be added to the reaction system in the form of an aqueous solution, respectively. In some cases, it can be added in the form of a solid. Further, in the first step, if necessary, the concentration of the mixed gel can be adjusted using pure water for the obtained mixed gel.
  • the silicate source, sodium compound, potassium compound, and titanium tetrachloride can be added in various addition orders.
  • a mixed gel can be obtained by adding titanium tetrachloride to a mixture of a silicate source, a sodium compound and / or a potassium compound, and water (this addition order is simply referred to as “additional order” hereinafter). (It may be called “Implementation of (1)”.)
  • the implementation of (1) is preferable in that the generation of chlorine from titanium tetrachloride is suppressed.
  • an aqueous solution of activated silicic acid obtained by cation exchange of alkali silicate, titanium tetrachloride and water
  • activated silicic acid obtained by cation exchange of alkali silicate, titanium tetrachloride and water
  • a sodium compound and / or a potassium compound is added to a mixture of these can also be employed.
  • a mixed gel can be obtained in the same manner as in the execution of (1) (this addition order may be simply referred to as “the execution of (2)” hereinafter).
  • Titanium tetrachloride can be added in the form of an aqueous solution or solid form.
  • sodium compounds and potassium compounds can also be added in the form of their aqueous solutions or solid forms.
  • the total concentration of sodium and potassium in the mixed gel is 0.5% by mass or more and 15% by mass or less, particularly 0.7% by mass in terms of Na 2 O. It is preferable to add so that it may become 13 to 13 mass%.
  • the total Na 2 O equivalent mass of sodium and potassium in the mixed gel and the total Na 2 O equivalent concentration of sodium and potassium in the mixed gel (hereinafter referred to as “total concentration of sodium and potassium (the potassium compound is used in the first step) If not, the sodium concentration) ”is calculated by the following formula.
  • the total concentration of sodium and potassium in the mixed gel is 6% by mass or less in terms of Na 2 O, so that the molar ratio of Ti: Si However, it is possible to effectively suppress the production of 1: 1 crystalline silicotitanate.
  • sodium silicate When sodium silicate is used as the silicate source, the sodium component in the sodium silicate simultaneously becomes the sodium source in the mixed gel. Therefore, the “Na 2 O equivalent mass (g) of sodium in the mixed gel” referred to here is counted as the sum of all sodium components in the mixed gel.
  • titanium tetrachloride stepwise or continuously as an aqueous titanium tetrachloride solution over a certain period of time in order to obtain a uniform gel.
  • a peristaltic pump etc. can be used suitably for addition of titanium tetrachloride.
  • the mixed gel obtained in the first step may be aged at 30 ° C. or more and 100 ° C. or less for 0.5 hours or more and 2 hours or less before performing the hydrothermal reaction which is the second step described later. From the viewpoint of obtaining a uniform product.
  • the aging step may be performed, for example, in a stationary state, or may be performed in a stirring state using a line mixer or the like.
  • the mixed gel obtained in the first step is subjected to a hydrothermal reaction as the second step to obtain crystalline silicotitanate.
  • the hydrothermal reaction is not particularly limited as long as the crystalline silicotitanate can be synthesized. Usually, it is preferably 120 ° C. or higher and 300 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 140 ° C. or higher and 180 ° C. or lower, preferably 6 hours or longer and 72 hours or shorter, more preferably 12 ° C. in an autoclave.
  • the reaction is carried out under pressure over a period of at least 36 hours.
  • the reaction time can be selected according to the scale of the synthesizer.
  • the water-containing crystalline silicotitanate obtained in the second step can be dried, and the obtained dried product can be pulverized or pulverized as necessary to form a powder (including granules).
  • the hydrous crystalline silicotitanate may be extruded from an aperture member in which a plurality of apertures are formed to obtain a rod-shaped molded body, and the obtained rod-shaped molded body may be dried to form a columnar shape.
  • the dried rod-shaped molded body may be formed into a spherical shape, or may be pulverized or pulverized into particles.
  • pulverization refers to an operation of loosening particles that are gathered into a lump
  • pulverization refers to an operation of applying mechanical force to the loosened solid particles to make them finer
  • the true circle equivalent diameter of the opening is preferably 0.1 mm or more and 10 mm or less, and more preferably 0.3 mm or more and 5 mm or less.
  • the true circle equivalent diameter here is a diameter of a circle calculated from the area when the area of one hole is a circle area.
  • the drying temperature after extrusion molding can be, for example, 50 ° C. or more and 200 ° C. or less.
  • the drying time can be 1 hour or more and 120 hours or less.
  • the dried rod-shaped molded body can be used as an adsorbent as it is, or may be used after being loosened. Moreover, you may grind
  • the powdery crystalline silicotitanate obtained by these various methods is preferably further classified and then used as an adsorbent from the viewpoint of increasing the adsorption efficiency of cesium and / or strontium.
  • a first sieve having a nominal opening prescribed in JISZ8801-1 of 1000 ⁇ m or less, particularly 710 ⁇ m or less.
  • it is also preferable to carry out using the 2nd sieve whose said nominal opening is 100 micrometers or more, especially 300 micrometers or more.
  • the crystalline silicotitanate obtained by the production method of the present invention has a general formula: Na 4 Ti 4 Si 3 O 16 .nH 2 O, (Na x K (1-x) ) 4 Ti 4 O 3 O 16 .nH 2 Crystalline silicon titanate represented by O and K 4 Ti 4 Si 3 O 16 .nH 2 O (wherein x represents a number greater than 0 and less than 1 and n represents a number from 0 to 8) Is at least one selected from
  • the first feature of the crystalline silicotitanate obtained by the production method of the present invention is that the molar ratio of Ti: Si is 4: 3, as is apparent from these general formulas.
  • the fact that the molar ratio of Ti: Si in the crystalline silicotitanate is this value can be confirmed by structural analysis of the crystalline silicotitanate by X-ray diffraction.
  • the second feature of the crystalline silicotitanate obtained by the production method of the present invention is that it does not contain titanium oxide as an impurity.
  • the crystalline silicotitanate obtained by the production method of the present invention has a general formula: Na 4 Ti 4 Si 3 O 16 .nH 2 O, (Na x K (1-x) ) 4 Ti 4 Si 3 O 16. nH 2 O and K 4 Ti 4 Si 3 O 16 ⁇ nH represented by 2 O Ti: molar ratio of Si of 4: mainly composed of what is 3, the other crystalline Shirikochitaneto You may contain in the range which does not impair the effect of invention. Further, it may contain by-products of titanate such as sodium titanate (Na 4 Ti 9 O 20 ) or its hydrate salt derived from this production method.
  • this titanate can rather be a component that improves the adsorption and removal properties of strontium, when used as an adsorbent that simultaneously removes cesium and strontium, this type of compound is a preferred by-product in the production method of the present invention. It can be said that there is.
  • the crystalline silicotitanate obtained by the production method of the present invention is excellent in the adsorption removal property of cesium and / or strontium.
  • the crystalline silicotitanate can be molded according to a conventional method if necessary, and the molded product obtained thereby can be suitably used as an adsorbent for cesium and / or strontium.
  • Examples of the molding process include granulation for forming a powdery crystalline silicotitanate or a powdery adsorbent containing it into a granular form, and slurrying a powdered crystalline silicotitanate to obtain calcium chloride, etc.
  • Examples thereof include a method in which a powdery crystalline silicotitanate or a powdery adsorbent containing the same is attached to the surface and / or the inside of the shaped substrate and fixed to form a sheet.
  • the granulation method include known methods such as stirring and mixing granulation, rolling granulation, extrusion granulation, crushing granulation, fluidized bed granulation, spray drying granulation (spray drying), and compression granulation.
  • a binder and a solvent may be added and mixed as necessary.
  • the binder known ones such as polyvinyl alcohol, polyethylene oxide, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose, starch, cornstarch, molasses, lactose, gelatin , Dextrin, gum arabic, alginic acid, polyacrylic acid, glycerin, polyethylene glycol, polyvinylpyrrolidone and the like.
  • the solvent various solvents such as an aqueous solvent and an organic solvent can be used.
  • the granulated product obtained by granulating the water-containing crystalline silicotitanate obtained by the production method of the present invention is suitable as an adsorbent for a water treatment system having an adsorption vessel and an adsorption tower filled with a radioactive substance adsorbent.
  • a water treatment system having an adsorption vessel and an adsorption tower filled with a radioactive substance adsorbent.
  • the shape and size of the granular product obtained by granulating the water-containing crystalline silicotitanate is filled in an adsorption vessel or packed tower, and treated water containing cesium and / or strontium is passed through. It is preferable to adjust the shape and size as appropriate so as to adapt to this.
  • a granular product obtained by granulating the water-containing crystalline silicotitanate obtained by the production method of the present invention is recovered by magnetic separation from water containing cesium and / or strontium by further containing magnetic particles.
  • magnetic particles include metals such as iron, nickel, and cobalt, or powders of magnetic alloys based on these metals, metal oxides such as iron trioxide, iron sesquioxide, cobalt-added iron oxide, barium ferrite, and strontium ferrite. Examples thereof include powders of magnetic system.
  • the granulation operation described above may be performed in a state where magnetic particles are contained.
  • the adsorbent of the present invention containing the crystalline silicotitanate and the titanate can be efficiently produced, but the adsorbent of the present invention comprises the crystalline silicotitanate and the above-mentioned It can also be produced by preparing the titanate separately and mixing it in any formulation.
  • X-ray diffraction Bruker D8 AdvanceS was used. Cu-K ⁇ was used as the radiation source. The measurement conditions were a tube voltage of 40 kV, a tube current of 40 mA, and a scanning speed of 0.1 ° / sec. ICP-AES: Varian 720-ES was used. The Cs and Sr adsorption tests were performed with a Cs measurement wavelength of 697.327 nm and a Sr measurement wavelength of 216.596 nm.
  • Standard samples used were Cs: 100 ppm, 50 ppm and 10 ppm aqueous solutions containing 0.3% NaCl, and Sr: 100 ppm, 10 ppm and 1 ppm aqueous solutions containing 0.3% NaCl.
  • Example 2 Sodium silicate 146 g was subjected to sodium removal treatment by cation exchange to obtain 1000 g of a 4.16% active silicic acid aqueous solution.
  • Amberlite IR-120B which is a weakly acidic cation exchange resin, was used.
  • To this active silicic acid aqueous solution 720.18 g of titanium tetrachloride aqueous solution was added over 4 hours and stirred to obtain a mixed aqueous solution.
  • To this mixed aqueous solution was added 1107.85 g of an aqueous caustic soda solution and stirred for 60 minutes to produce a mixed gel.
  • Example 3 in this X-ray diffraction chart, the main peak of crystalline silicotitanate and the main peak of sodium titanate were detected in the same diffraction angle range as that of the adsorbent obtained in Example 1. .
  • the obtained adsorbent (crystalline silicotitanate) was subjected to the same analysis and adsorption test as in Example 1.
  • the composition judged from the X-ray diffraction structure of the obtained adsorbent is shown in Table 1 below.
  • Table 2 shows the height ratio of the main peak obtained from FIG. 3 and the molar ratio obtained by composition analysis.
  • the results of the adsorption test for Cs and Sr are shown in Table 3 below.
  • Example 3 A mixed gel was produced in the same manner as in Example 1 except that the amount of pure water added in the mixed gel was 361.30 g, and an adsorbent (crystalline silicotitanate) was produced from the mixed gel.
  • the concentration of SiO 2 in the mixed gel was 1.67%, the concentration of TiO 2 was 4.36%, and the sodium concentration in terms of Na 2 O was 2.51%.
  • FIG. 4 shows an X-ray diffraction chart after baseline correction of the obtained adsorbent. As shown in FIG.
  • Example 4 in this X-ray diffraction chart, the main peak of crystalline silicotitanate and the main peak of titanate were detected in the same diffraction angle range as that of the adsorbent obtained in Example 1.
  • the obtained adsorbent (crystalline silicotitanate) was subjected to the same analysis and adsorption test as in Example 1.
  • the composition judged from the X-ray diffraction structure of the obtained adsorbent is shown in Table 1 below.
  • Table 2 shows the height ratio of the main peak obtained from FIG. 4 and the molar ratio obtained by the composition analysis.
  • the results of the adsorption test for Cs and Sr are shown in Table 3 below.
  • the concentration of SiO 2 in the mixed gel was 2.47%, the concentration of TiO 2 was 6.46%, and the sodium concentration in terms of Na 2 O was 3.32%.
  • the obtained adsorbent (crystalline silicotitanate) was subjected to the same analysis and adsorption test as in Example 1.
  • FIG. 5 shows an X-ray diffraction chart after baseline correction of the obtained adsorbent (crystalline silicon titanate).
  • the composition judged from the X-ray diffraction structure of the obtained adsorbent (crystalline silicotitanate) is shown in Table 1 below. As a result, the presence of titanium oxide as an impurity was confirmed.
  • the results of the adsorption test for Cs and Sr are shown in Table 3 below.
  • the concentration of SiO 2 in the mixed gel was 2.8%, the concentration of TiO 2 was 7.4%, and the total concentration of sodium and potassium in terms of Na 2 O was 3.5%.
  • Example 1 adsorbent (crystalline silicon titanate) obtained in Example 1 was subjected to an adsorption test for Cs and Sr under the same conditions as the adsorbent obtained in Example 6 (crystalline silicotitanate). This is also shown in Table 6.
  • Example 7 to 10 The slurry obtained by the hydrothermal reaction in the second step of Example 1 was washed and adjusted to a moisture content of 69.5% (solid content: 30.5%).
  • This water-containing crystalline silicotitanate was put into a cylindrical hand-push extruder equipped with a screen having a true circle equivalent diameter of 0.5 mm at the tip, and extrusion-molded.
  • the water-containing molded body extruded from the screen was dried at normal pressure for 1 day at the temperature shown in Table 7 below.
  • the obtained dried product was lightly pulverized in an agate mortar.
  • the obtained pulverized product was passed through a sieve having an opening of 710 ⁇ m.
  • the sieve was pulverized again, and all the pulverized material was passed through a sieve having an opening of 710 ⁇ m.
  • the sieve was collected and passed through a sieve having an opening of 300 ⁇ m.
  • the sieve top was collected and used as a sample.
  • Example 11 A sample was obtained in the same manner as in Example 9, except that the dried product obtained from the water-containing molded product was not pulverized, but was put in a PP (polypropylene) bag and crushed by lightly tapping with a rubber hammer. However, after the crushed material was passed through a sieve having an opening of 710 ⁇ m, the sieve was not further pulverized, and only the material that passed through the sieve having an opening of 710 ⁇ m by crushing was passed through a sieve having an opening of 300 ⁇ m. The sieve top was collected and used as a sample.
  • PP polypropylene
  • Example 12 A sample was obtained in the same manner as in Example 9 except that an extrusion molding machine equipped with a screen having a perfect circle equivalent diameter of 1.5 mm was used instead of the screen having a hole diameter of 0.5 mm.

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CA2939521A1 (en) 2015-10-01
US20160107140A1 (en) 2016-04-21
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RU2016137781A (ru) 2018-04-27
EP3098817A4 (de) 2017-10-18
JP2015188782A (ja) 2015-11-02
US9486776B2 (en) 2016-11-08
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US20170021329A1 (en) 2017-01-26
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